TW200918638A - Organic el device - Google Patents

Abstract

A light-emitting layer of an organic EL device is composed of a host containing chrysene and a dopant containing benzidine. By having such a constitution, the energy gap of the dopant is increased and the affinity level of the dopant becomes lower than the affinity level of the host. Consequently, the organic EL device is able to have a shorter wavelength for blue light emission and a longer life.

Description

200918638 IX. Description of the Invention [Technical Field of the Invention] The present invention relates to an organic EL element. [Prior Art] It is known that an organic light-emitting layer is provided between an anode and a cathode, and an organic electroluminescent element (organic EL) which emits light by an exciton energy generated by recombination of a hole in which an organic light-emitting layer is injected and electrons is recombined. element). Such an organic electroluminescence device can be used as a self-luminous device. It is expected to be a light-emitting device which is excellent in luminous efficiency, image quality, power consumption, and thin design. When a luminescent material is utilized in an organic EL element, a blending of the blended material in the host material is known. However, since the injected energy can efficiently generate the agonist while efficiently correlating the agonist energy with luminescence, the agonist energy generated by the principal component is moved to the blend, and the self-blend is used. The composition of the luminescence can be obtained. At this time, when the intrinsic component to the blend undergoes intermolecular energy shift, the energy gap E g 主 of the main component must be larger than the energy gap E g D of the blend. However, in recent years, in the dark blue luminescent color which is desired to be short-wavelength, there is no combination with the optimum host material of such a deep blue luminescent blend. It is disclosed in Document 1 (Patent Publication No. 2004-75567) that a blue element having a broad energy gap main material and an arylamine-based blend is used, but the element life is not necessarily sufficient. Moreover, even if the illuminating color is short-wavelength blended material-5-200918638, there are several kinds of materials, and the energy movement of the bismuth-based main material 'independent component to the blend which is generally used does not proceed, resulting in The problem of luminescence from the blend cannot be obtained. The main object of the present invention is to provide an organic EL device that achieves a short-wavelength and a long-life of a blue light-emitting wavelength. [Inventors] The present inventors have solved the related problems and studied the results in detail. As a blend having a large energy gap of a short wavelength which achieves a blue light-emitting wavelength, a benzidine-containing or a caver can be used. Therefore, in order to cause such a blend to emit light, as a main component having a higher affinity level and a larger energy gap than the blend, the use of a cavern can achieve a long life. Here, the energy gap is a difference between the conduction level and the valence electron level, and can be defined, for example, by the absorption end of the absorption spectrum in benzene to the measurement enthalpy. Specifically, the absorption spectrum was measured using a commercially available visible ultraviolet spectrophotometer, and the wavelength at which the absorption spectrum was excited was calculated. However, the present invention is not limited to the above-described regulations, and may be defined as a band gap without departing from the gist of the present invention. Further, the so-called affinity level Af (electron affinity) indicates the energy released or absorbed when a molecule of a material imparts one electron, and the release is defined as a negative definition of positive absorption. The affinity level Af is defined by the ionization potential Ip and the optical energy gap Eg as -6-200918638.

Af=Ip-Eg wherein the ionization potential Ip is an energy required for taking out electrons from the compound of each material to ionize it, for example, in the present case, an ultraviolet photoelectron spectroscopic analyzer (AC-3, chemistry) ) Measured by the meter. However, the present invention is not limited to the above-described regulations, and may be defined as an affinity level without departing from the gist of the present invention. The present invention has been completed in accordance with the relevant findings. In other words, the organic EL device of the present invention is an organic EL device in which an organic thin film layer composed of at least one or a plurality of layers of a light-emitting layer is sandwiched between a cathode and an anode, and the light-emitting layer is characterized by the following formula (1). The main component shown is a blend of the following general formula (2).

In the general formula (1), R1 to R12 represent a hydrogen atom or a substituent. However, at least one of the nuclear carbon numbers 6 R to R in 200918638 each independently represents a substituted or unsubstituted aryl group of ~60.

In the general formula (2), Ari to Ar4 each independently represent an aryl group having a core carbon number of 6 to I4. L1 represents a substituted or unsubstituted benzene skeleton 'naphthalene skeleton, skeleton. P is an integer of 1 to 6, and when ρ is 2 or more, 1^ is different or different. Further, when ρ is 2 or more, the substitution positions of Li are different or different. S is 〇 or 1. Further, in the organic EL device of the present invention, the above-mentioned general formula (2) may be represented by the following general formula (3). Or unsubstituted skeleton, phenanthrene can be the same, can be the same, replace the aforementioned

In the general formula (3), Ar5 to Ar8 each independently represent a phenyl group, a naphthyl group or a phenanthryl group. Each of L2 and L3 independently represents a substituted benzene skeleton, a naphthalene skeleton, and a phenanthrene skeleton. In the organic EL device of the present invention, the above-mentioned main component is preferably represented by the general formula (4).

Ar9-Ch-Ar10 · · · (4) In general formula (4), 'Ch denotes a substituted or unsubstituted cave skeleton, and Ar1() each independently represents a substituted or unsubstituted aryl group having a carbon number of 6 to 14 or A substituent consisting of a plurality of combinations. The invention is based on the fact that the use of a benamine or a cave as a blend constituting the light-emitting layer uses an organic EL element f which has a short-wavelength and long life of the blue light-emitting wavelength. The reason why the main material and the biologic material of the present invention are extended by the combination of the present invention is not absolute, but it can be roughly considered. The blend material of the present invention is intended to have an aromatic amine in the short-wavelength blue light-emitting material structure. As a result, the ionization potential becomes large and the energy gap becomes large, so that a shorter wavelength blue luminescence can be obtained. However, considering that the amine contained in the complex is not high for electrons, if the electron is directly injected when the element is driven, the molecule becomes inferior to the life. For this reason, in the present invention, the affinity level of the main component is small, and the affinity level of the compound is small, so that electrons are not easily injected directly into the doping. Next, the Ar9 group contains: 〇, although it is reasonable to be resistant to the blend -9 - 200918638, thereby preventing the degradation of the blend and prolonging the life of the component, enabling short-wavelength luminescence And it is a long-life component. In the past, as the main material of the light-emitting compound, only the main material having a higher energy gap than the light-emitting blend was selected. That is, it is only considered that the main material having a smaller affinity level and a larger ionization potential than the blend is selected. With such a configuration, when a charge is injected into the main component of the blend, a part of the injected charge is not a main component, and the blend is directly implanted with 0, for example, 'in view of injecting electrons into the light-emitting layer, Blends with a higher affinity level than the main component are also easy to inject electrons. In particular, when the main component and the blend are both enlarged in energy gap in order to shorten the wavelength, the gap from the electron transport layer to the main component becomes large, and electrons are easily injected into the blend. Therefore, when a short-wavelength blue light-emitting blend is simply blended into a wide-gap main component, there is a problem that the life of the element is extremely short. In this regard, in the present invention, the affinity level of the blend is made smaller than the affinity level of the main component, and it is difficult to form a combination of the main component and the blend which are directly injected into the blend. With such a configuration, it is possible to realize a blue light-emitting light having a shorter wavelength than in the past and an unprecedented long-life element. Further, in the present invention, the energy gap of the main component of the light-emitting layer becomes large, and the ionization potential Ip also becomes large. Therefore, the difference in 1P between the main material and the hole injection and the transport layer becomes large. -10- 200918638 makes it difficult to inject the hole in the light-emitting layer, and the driving voltage for which sufficient brightness is to be obtained may rise. In such a case, it is preferable to add a charge injection auxiliary agent to the light-emitting layer to alleviate the injection barrier of the hole. As such a charge injection auxiliary agent, it is possible to use hole injection. Transport material. Embodiments of the invention Hereinafter, embodiments of the present invention will be described. [Configuration of Organic EL Element] First, the element configuration of the organic electroluminescence element will be described. As a representative element of the organic electroluminescence element, (1) anode/light-emitting layer/cathode (2) anode/hole injection layer/light-emitting layer/cathode (3) anode/light-emitting layer/electron injection layer/cathode (4) Anode/hole injection layer/light-emitting layer/electron injection layer/cathode (5) anode/organic semiconductor layer/light-emitting layer/cathode (6) anode/organic semiconductor layer/electron barrier layer/light-emitting layer/cathode (7) Anode/organic semiconductor layer/light-emitting layer/adhesion improving layer/cathode (8) anode/hole injection layer/hole transport layer/light-emitting layer/electron injection layer/cathode (9) anode/insulation layer/light-emitting layer/insulation Layer/Cathode (10) Anode/Inorganic Semiconductor Layer/Insulation Layer/Light Emitting Layer/Insulation Layer/Cathode-11 - 200918638 (11) Anode/Organic Semiconductor Layer/Insulation Layer/Light Emitting Layer/Insulation Layer/Cathode (12) Anode/ Insulation layer/hole injection layer/hole transport layer/light-emitting layer/insulation layer/cathode (1 3 ) anode/insulation layer/hole injection layer/hole transport layer/light-emitting layer/electron injection layer/cathode structure Give it. The organic EL device of the present embodiment preferably includes at least an anode, a hole injection layer, a light-emitting layer, an electron transport layer, and a cathode sequence. Although it is preferable to use the general (8) configuration, it is undoubtedly not limited thereto. (Translucent Substrate) The organic electroluminescence device is fabricated on a light-transmitting substrate. The light-transmitting substrate is preferably a substrate supporting an organic electroluminescence device, and a smooth substrate having a light transmittance of 50 to 700 nm in a visible light region of 400 to 700 nm is preferable. Specifically, a glass plate, a polymer plate, etc. are mentioned. Specific examples of the glass plate include soda lime glass, barium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium boric acid glass, and quartz. Further, examples of the polymer sheet include polycarbonate, acryl, polyethylene terephthalate, polyacid sulfide, and polyfluorene. (Anode) The anode of the organic electroluminescence element is effective in injecting a hole into a hole -12-200918638 injection layer, a hole transport layer or a light-emitting layer, and has a work function of 4.5 eV or more. Specific examples of the anode material include indium tin oxide alloy (ITO), tin oxide (NESA), indium zinc oxide, gold, silver, platinum, copper, and the like. Further, as the anode, for the purpose of injecting electrons into the electron transport layer or the light-emitting layer, a material having a small work function is preferable. The anode can be produced by forming these electrode materials into a film by a vapor deposition method or a sputtering method. When the light emission from the light-emitting layer is taken out from the anode in this manner, it is preferable that the light transmittance of the visible light region of the anode is larger than 10%. Further, the sheet resistance of the anode is preferably several hundred Ω / □ or less. The film thickness of the anode is generally selected from the range of 1 Onm to 1 μm, preferably 10 to 200 nm, depending on the material. (Light Emitting Layer) The light emitting layer of the organic electroluminescence element has the following functions. That is, (1) injection function; when the electric field is applied, the anode or the hole injection layer can be injected into the hole, the cathode or the electron injection layer can inject electrons, (2) the transport function; and the injected charge (electron) And the function of the electric hole to move it by the electric field force, (3) the illuminating function; providing a recombination place of the electron and the hole, and the function of the illuminating connection. However, the ease of injection of the hole and the ease of electron injection may have a difference, and the transport energy of the hole and the mobility of the electron may also differ. As a method of forming the light-emitting layer, for example, a known method such as a vapor deposition method, a rotation method of -13-200918638, or an LB method can be applied. The light-emitting layer is preferably a molecular deposition film. The molecular deposition film is a film formed by precipitation of a material compound in a gas phase state, or a film formed by curing a material compound in a solution state or a liquid phase state. Generally, the molecular deposition film can be obtained by the LB method. The formed film (molecular accumulation film) is distinguished by a difference in agglomerated structure, high-order structure, or functional difference caused by it. In the case of dissolving a binder such as a resin and a material compound in a solvent to form a solution, the film is formed by a spin coating method or the like, as disclosed in Japanese Laid-Open Patent Publication No. Hei. A light-emitting layer can also be formed. Further, the film thickness of the light-emitting layer is preferably from 5 to 50 nm, more preferably from 7 to 50 nm, most preferably from 1 to 50 nm. When the thickness is less than 5 nm, it may be difficult to form a light-emitting layer, and the adjustment of the chromaticity is difficult. If it exceeds 50 nm, the driving voltage may increase. In the organic EL device of the present embodiment, the light-emitting layer contains a main component and a blend. However, specific examples of the main component include the compounds represented by the following general formula (5). -14- 200918638

In the general formula (5), R1 to R12 represent a hydrogen atom or a substituent. However, at least one of 'R 1 to R 1 2 each independently represents a substituted or unsubstituted aryl group having a core carbon number of 6 to 60. Examples of the aryl group having a core carbon number of 6 to 60 include a phenyl group, a naphthyl group, a phenanthryl group, a biphenyl group, a terphenyl group, a tetracene group, a fluorenyl group, a methyl fluorenyl group, and a dibenzofluorenyl group. , fluoranthenyl, binaphthyl, phenylnaphthyl, porphyrin, benzophenanthrenyl, benzopyrylene, triphenylene and the like. Preferably, the aryl group having a core carbon number of 6 to 14 is preferably a phenyl group, a biphenyl group, a naphthyl group or a phenanthryl group. Further, specific examples of the general formula (5) include the compounds represented by the following general formula (6).

Ar9—Ch—Ar10 . . . (6) In general formula (6), Ch represents a substituted or unsubstituted anthracene skeleton, and Ar9 'ArIG each independently has a substituted or unsubstituted aryl group having a carbon number of 6 to 14; Substituents consisting of singly or in combination. Examples of the aryl group having a nucleus carbon number of 6 to 14 include a phenyl group, a naphthyl group, and a -15-200918638 phenanthryl group and an anthracenyl group. When these aryl groups are combined in a plural number, examples thereof include a biphenyl group, a terphenyl group, a naphthylphenyl group, a phenylnaphthyl group, a binaphthyl group, a phenanthrylphenyl group, and a phenanthryl group. Among them, biphenyl, naphthylphenyl and phenanthrylphenyl are also preferred. Further, specific examples of the main component include compounds represented by the following general formulas (7) to (11).

Ar1—Ch—Ar2 · · · (7) In the general formula (7), Ch represents a substituted or unsubstituted cave skeleton, and Ar1 and Ar2 each independently represent a substituted or unsubstituted aryl group having a core carbon number of 6 to 14 as a single Or a combination of substituents. However, Ar^Ar2, Ar1, and Ar2 do not benefit. When it contains onions, the crystallinity is sometimes too high. Specific examples of the aryl group having a core carbon number of 6 to 14 and the combination are as described above.

• (8) In the general formula (8), 'Ar1 and Ar2 each independently represent a substituent of a substituted or unsubstituted aryl group having a carbon number of 6 to -4, which is a combination of singly or plural, -16-200918638. However, Ar^Ar2, Ar1, and Ar2 do not contain ruthenium. R1 to r1g represent a hydrogen atom or a substituent. When ruthenium is contained, the crystallinity may be too high. Specific examples of the aryl group and the combination of the core carbon number of 6 to 14 are as described above.

An unsubstituted or unsubstituted naphthalene, an aromatic unsubstituted phenanthrene, and Ar4 represents a substituted or unsubstituted group having a carbon number of 6 to 4, which is composed of a single or plural combination: M ^ 祖〇 Substituent. R丨~R1 1 represents a hydroquinone or a substituent. k is 1~4, Rii

The integer of ^. Further, when k is 2 or more, R may be the same or in phase with each other.桉 艚 ^ The aryl group having a nucleus number of δ 〜 14 and the combination thereof are as described above.

-17- 200918638 In the general formula (10), Ar4 and Ar5 each independently represent a substituent composed of a substituted or unsubstituted aryl group having 6 to 14 carbon atoms in a single or plural combination. However, ArkAr5, Ar4, and Ar5 do not contain hydrazine. R1 to R12 represent a hydrogen atom or a substituent. k is an integer of 1 to 4. Further, when k is 2 or more, R11 may be the same or different from each other. 1 is an integer of 1 to 4. When 1 is 2 or more, R12 may be the same or different from each other. When ruthenium is contained, the crystallinity may be too high. Specific examples of the aryl group having a core carbon number of 6 to 14 and the combination are as described above. D22 R23 d24 ο 25

R28 RW In the general formula (11), Ar6 and Ar7 each independently represent a substituent composed of a substituted or unsubstituted aryl group having 6 to 14 carbon atoms in a single or plural combination. However, 'Ar6#Ar7' Ar6 and Ar7 do not contain strontium. R21 to R3g represent a hydrogen atom or a substituent. When ruthenium is contained, the crystallinity may be too high. Specific examples of the aryl group having a core carbon number of 6 to 14 and the combination are as described above. Among them, in the general formulae (7) and (8), the structure in which 'Ar1 is a substituted or unsubstituted naphthalene, a substituted or unsubstituted phenanthrene is preferable from the viewpoint of heat resistance, and in the general formula (11), R21 When at least one of R3G is a substituted or unsubstituted aryl group having 5 to 14 carbon atoms, R22 and R27 are each independently substituted or unsubstituted aryl group having a core carbon number of 6 to 14 in a single or multiple combination. The composition of the substituents constituting -18-200918638 is preferable. The substituent in the above general formulae (5) to (11) may, for example, be an alkyl group (preferably having a carbon number of from 1 to 20', more preferably a carbon number of from 1 to 12, particularly preferably an alkyl group of from 1 to 8 carbon atoms. Examples of the group include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a η-octyl group, an η-fluorenyl group, an η-hexadecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like. And an alkenyl group (preferably a carbon number of 2 to 20, more preferably a carbon number of 2 to 12, particularly preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a 2-butenyl group. , 3-pentenyl, etc.), alkynyl group (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 12, particularly preferably an alkynyl group having 2 to 8 carbon atoms, and examples thereof include propynyl group; , 3 -pentynyl, etc.), aryl (preferably a carbon number of 6 to 20, particularly preferably an aryl group of 6 to 14, for example, a phenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group), or a hetero group The ring group (preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms) may, for example, be an imidazyl group, a pyridyl group, a quinolyl group, a furyl group, a thienyl group or a piperidinyl group. , morpholino, benzoxazolyl, benzimidazolyl, benzothianyl, oxazolyl, benzofuranyl, dibenzofuranyl, And a thiophenyl group, a dibenzothiophenyl group, etc., a substituted or unsubstituted amine group (preferably having a carbon number of 0 to 20, more preferably a carbon number of 0 to 12, particularly preferably an amine having a carbon number of 66) Examples of the group include an amine group, a methylamino group, a dimethylamino group, a diethylamino group, a diphenylamino group, a diphenylmethylamino group, and the like, and an alkoxy group (preferably having a carbon number of 1 to 2 Å, more preferably The alkoxy group having a carbon number of 1 to 12' is particularly preferably a carbon number of 1 to 8, and examples thereof include a methoxy group (e.g., a methoxy group, an ethoxy group, a butoxy group, etc.) (preferably a carbon number of 6~) 2〇' is more preferably a carbon number of 6 to 16', particularly preferably an aryloxy group having 6 to 12 carbon atoms, and examples thereof include a phenoxy group and a 2-naphthyloxy group, and a mercapto group (preferably carbon). Number 丨~" 'More preferably carbon number 1~16, especially good for carbon number ι~12 sulfhydryl group, for example *19- 200918638 cites ethyl ketone group, benzamidine group, formazan group, trimethyl group Ethyloxycarbonyl (e.g., preferably a carbon number of 2 to 20', more preferably a carbon number of 2 to 16, and particularly preferably an alkoxycarbonyl group having a carbon number of 2 to 12, for example, a methoxycarbonyl group; Ethoxycarbonyl, etc., aryloxycarbonyl (preferably carbon number 7 to 20' is more preferably carbon number 7 to 16, particularly preferably carbon number 7 Examples of the aryloxycarbon group of ～10 include, for example, a phenoxycarbonyl group, and an alkoxy group (preferably having a carbon number of 2 to 20 Å, more preferably a carbon number of 2 to 16, and particularly preferably a carbon number of 2 to 1 Å). Examples of the decyloxy group include an acetic acid oxy group and a phenyl ethoxy group, and a guanamine group (preferably, the carbon number is 2 to 20', more preferably a carbon number of 2 to 1, and particularly preferably a carbon number of 2 to 1. Examples of the hydrazine amide group include an acetamino group, a benzylamino group, and the like, and an oxycarbonylamine group (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 1,6). Preferred examples of the alkoxycarbonylamino group having 2 to 12 carbon atoms include a methoxylamine group and the like, and an aryloxycarbonylamino group (preferably having a carbon number of 7 to 2 Å, more preferably carbon). The number is from 7 to 16, particularly preferably an aryloxyamine group having a carbon number of 7 to 12, and, for example, a phenoxycarbonylamino group, a substituted or unsubstituted sulfonylamino group (preferably a carbon number of 1 to 2) 20, more preferably a carbon number of 1 to 16, particularly preferably a sulfonylamino group having 1 to 12 carbon atoms, for example, a methanesulfonylamino group or a benzenesulfonylamino group, a substituted or unsubstituted amine. a sulfonyl group (preferably having a carbon number of 〇20 to 20, more preferably a carbon number of 11 to 1,6, particularly preferably an amine sulfonyl group having a carbon number of 11 to 1,2, For example, an amine sulfonyl group, a methotrexate group, a dimethylamine sulfonyl group, an aniline sulfonyl group, etc., a substituted or unsubstituted aminomethyl fluorenyl group (preferably, a carbon number of 1 to 20, more Preferably, the carbon number is from 1 to 16, particularly preferably from 1 to 12 carbon atoms, and examples thereof include an aminomethyl fluorenyl group, a methylaminomethyl fluorenyl group, a diethylaminomethyl fluorenyl group, and an anilino group. a mercapto group or the like), an alkylthio group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 16', particularly preferably an alkylthio group having a carbon number of 1 to 12, for example, -20-200918638 A methylthio group, an ethylthio group or the like, an arylthio group (preferably having a carbon number of 6 to 20, more preferably a carbon number of 6 to 16, particularly preferably an arylthio group having a carbon number of 6 to 12) For example, a phenylthio group or the like, a 'substituted or unsubstituted sulfonyl group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 16, particularly preferably a carbon number of 1 to 12; The base may, for example, be a methylsulfonyl group or a p-toluenesulfonyl group, or a substituted or unsubstituted sulfinyl group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 16). Examples of the arylene group having 1 to 12 carbon atoms include a sulfinyl group and a sulfinyl group. The substituted or unsubstituted ureido group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 16, particularly preferably a carbon number 丨~2), for example, a ureido group or a methylureido group , phenylureido group, etc., substituted or unsubstituted guanidinium phosphate group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 丨6', particularly preferably a phosphonium amino group having a carbon number of 1 to 12 Examples thereof include diethyl ethyl acetonate, phenyl phosphonium amide, etc., a thiol group, a thiol group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, a spider atom), and a cyano group. a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, a sulfinyl group, a hydrazino group, an imido group or a heterocyclic group (preferably a heterocyclic group having a carbon number of 1 to 30, more preferably a carbon number of 1 to 12) 'As the hetero atom, for example, a nitrogen atom, an oxygen atom or a sulfur atom may be mentioned, and specific examples thereof include an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a thienyl group, a piperidinyl group, and a morpholino group. , benzoxazolyl, benzimidyl, benzothiazolyl, oxazolyl, benzofuranyl, dibenzofuranyl 'exidothiophenyl, dibenzothiophenyl, etc.), formane Base The carbon number is 3 to 4 Å, more preferably 3 to 30 carbon atoms, and particularly preferably a carbon number of 3 to 24, and examples thereof include a trimethylmethanyl group and a triphenyl methacrylate group. ) Wait. These substituents may be further substituted. Further, the substituents may be the same or different when they are two or more -21 - 200918638. Further, depending on the case, they may be joined to each other to form a loop. Among the above, an alkyl group, an alkenyl group or an aryl group is preferred. Further, the specific compounds represented by the general formulae (5) to (1 1 ) are as follows: 7]

-22- 200918638

-23- 200918638

-24- 200918638

%

-25- 200918638

Further, specific examples of the blend include the compounds represented by the following general formula (12). -26- (12) (12)200918638

In the general formula (12), each of Ar1 to Ar4 is an unsubstituted or unsubstituted aryl group having 6 to 14 carbon atoms. 1^ represents a substituted or unsubstituted benzene skeleton, a naphthalene skeleton, an anthracene skeleton, or a phenanthrene skeleton. P is an integer of 1 to 6, and when 1) is 2 or more, L1 may be the same or different from each other. Further, when p is 2 or more, the substitution positions of each other may be the same or different. s is 〇 or i. P is preferably an integer of from 1 to 4. Further, when L1 is a substituted or unsubstituted benzene skeleton, that is, a substituted or unsubstituted phenyl group, p is preferably an integer of 2 to 4, and an aryl group having a nucleus number of 6 to 14 is exemplified by a phenyl group. , naphthyl, anthracenyl, non-yl, biphenyl, and the like. Phenyl, naphthyl or biphenyl is preferred. The aryl group may be substituted, and the specificity of the substituent is, for example, the above. Among them, those substituted with an alkyl group or an aryl group are preferred. Among the other compounds represented by the general formula (1 2 ), the affinity level is 2_4 eV as shown below. When such a compound is used in a blend, it is difficult to directly inject the electrons into the blend, and it is preferable from the viewpoint of preventing deterioration of the blend and prolonging the life of the organic EL device. -27- 200918638

Ί-〇-〇~

-O-Q-

Ν-0~0~

\ & \ un3 ρ ^ ύ ύ H3C CH3 H3C CH3 H3C CH3 H3c CH3 h3c ch3 h3c ch3 H3C-Q 0-CH3 h3c ch3 h3c ch3 h3c- ch3 H3Q-CH3 H3C-PH3 h3c h3c- ch3

SI H3C

\~QrOr _ch3

Further, among the other compounds represented by the general formula (12), the affinity level is 2.5 eV as shown below. When such a compound is used in a blend, it is difficult to directly inject the electrons into the blend, and it is preferable from the viewpoint of preventing deterioration of the blend and prolonging the life of the organic EL device. -28- 200918638

H3c ch3 ch3 h3c ch3 H3〇^ch3 ch3

N h3c

H3c h3c ch , , CH3 Q h3c ch3 H3C^ ch3 H3Cv pH3

H3c 0 h3c ch3 h3c ch3 h3c d _ w b

Ch3 ch3

Ch3 h3c ch3 h3c ch3

•29- 200918638

Further, as the blend, in place of the compound represented by the above general formula (1 2 ), the compound represented by the following general formula (13) can be used. -30- • * * (13) 200918638

In the general formula (13), 'Ar5 to Ar8 each independently represent a substituted or unsubstituted phenyl group, a naphthyl group, or a phenanthrenyl group. Each of L2' L3 independently represents a substituted or unsubstituted benzene skeleton, a naphthalene skeleton, or a phenanthrene skeleton.

Ar5 to Ar8, L2, and L3 may be substituted, and specific examples of the substituent are as described above. Among them, those substituted with an alkyl group or an aryl group are preferred. However, by constituting a light-emitting layer containing a main component containing the above-mentioned cavity and a blend containing benzidine or B, the gap of the blend is made larger, and the affinity level of the blend is lowered to It is lower than the affinity level of the main component. Thereby, the short-wavelength and long-life of the blue light-emitting wavelength can be achieved (the hole injection/transport layer (hole transport region)). The hole injection/transport layer contributes to the injection of the hole in the light-emitting layer. The layer is transported to the light-emitting area, the hole mobility is large, and the ionization energy _^ is less than 5_5eV. As such a hole injection and transport layer, it is preferable to transport the hole to the light-emitting layer at a lower electric field strength, and the mobility, for example, an electric field of 1 〇 4 〜 1 〇 6 v / cm is applied, only @Ί里L〇-4cm2/V • Second is better. The material is formed as such a hole injection layer or a hole transport layer - 31 - 200918638 Specific examples include a triazole derivative (refer to the specification of U.S. Patent No. 3,112,197, etc.), and an oxadiazole derivative (US Patent No. 3,189,447) For the reference of the specification, the imidazole derivative (for reference), and the polyarylalkane derivative (U.S. Patent No. 3,6,5,042, the same as the third, 820, 9) No. 89, No. 3, 542, No. 5, 44, No. 3, 542, No. 45-555, No. 51-10983, Japanese Patent Laid-Open No. 51-93224, No. 55-17105, and No. 56-4148 Japanese Patent Publication No. 55-108667, Japanese Patent Application Laid-Open No. 55-156953, No. 56-36656, etc., and pyrazoline derivatives and pyrazole derivatives (U.S. Patent No. 3,180,729, the same as 4,278,74) No. 6 of the specification, Japanese Patent Laid-Open No. 5-5-8 8064, the same as Japanese Patent No. 5-88 065, the same as 49-105 5 3, the same as 5 5-5 1 086, the same as 5 6-8005 Japanese Patent Publication No. 1, the same as No. 56-88141, the same as No. 57-45545, the same as No. 54-1 1 2 63 7 , the same as 5 5 - 7 Reference No. 4546, etc., and phenyldiamine derivatives (U.S. Patent No. 3,615, No. 4, No. 4, Japanese Patent Publication No. 51-10105, the same as No. 46-37 1 2, the same as 47-253 3 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The same as No. 3,240,597, the same as No. 3,658,520, the same as No. 4, 232, 103, the same as No. 4, 175, 96, the same as the fourth, 〇1 2, 3 76, special public 49 -35702, Japanese Patent Publication No. 39-27577, Japanese Patent Application Laid-Open No. Hei 55-144250, No. 56-119132, the same as No. 56-22U7, and No. 1,10,518 of the West German Patent No. -32-200918638 The book is referred to as a reference), the amine-substituted Chalcone derivative (refer to the specification of U.S. Patent No. 3,526,50, etc.), and the oxazole derivative (the disclosure of the specification of U.S. Patent No. 3,25,7,203, etc.) ), a styrene-based hydrazine derivative (for reference), and an anthrone derivative (Japanese Patent Publication No. 5-6-4623) Japanese Patent Laid-Open No. 5 4 - 1 1 0 8 3 No. 7 and the like), anthracene derivatives (U.S. Patent No. 3,7,7,462, and JP-A-54-5-9 1 43, the same as 5 5 - Japanese Patent Publication No. 5-20-63, the same as Japanese Patent Application Publication No. 55-46760, the same as Japanese Patent Application No. 55-46760, the same as 5 5-8 5495, the same as the 57-1 1 3 50, the same as 57-148749, and the special Kaiping 2- 311,591, and the like, and a stilbene derivative (Japanese Unexamined Patent Publication No. Hei 61-210363, No. 61-22845 No., No. 61-14642, No. 61-72255, the same as 62) -47646, Japanese Patent Publication No. 62-36674, Japanese Patent Publication No. 62-1 0652, Japanese Patent Publication No. 62-3025, No. 60-93 45 5, the same as No. 60-94462, the same as 60- 1 74749 No. 60- 1 7 5 〇 52, etc.), decazane derivatives (U.S. Patent No. 4,95, 905), polydecane system (Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei. A conductive polymer oligomer (particularly a thiophene oligomer) disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. As the material of the hole injection layer or the hole transport layer, the above-mentioned, porphyrin compound (except as disclosed in JP-A-63-295695), an aromatic tertiary amine compound, and a styrylamine compound can be used. U.S. Patent No. 4,127,412, Japanese Patent Laid-Open No. Sho 53-2703 No. 3, the same as No. 54_5 844 5, the same as No. 54-丨4963 4, the same as 54-642 " No. -33-200918638, the same 5 5 -794 5 Japanese Patent Laid-Open No. Hei. No. 5-5-1 442, No. 56-119132, No. 61-295558, No. 61-98353, and No. 63-295 695, etc. An aromatic tertiary amine compound is used. Further, in the case of having two condensed aromatic rings in the molecule described in U.S. Patent No. 5,061,569, for example, 4,4'-bis(N-(1-naphthyl)-N-anilino)biphenyl (hereinafter) The abbreviated as "NPD", the 4,4',4"-parameter (N-(3-methyl) which is linked by a starburst type in the three triphenylamine units described in Japanese Patent Publication No. 4-3 08688 Phenyl)-N-anilino) triphenylamine group. Further, the hexaazatribenzophenone derivative described in Patent Publication No. 36144〇5, 3571977 or U.S. Patent No. 4,780,536 can also be used as a hole injecting material. In addition to the aromatic secondary methyl compound as the material of the light-emitting layer, an inorganic compound such as p-type Si or p-type SiC may be used as a material for the hole injection layer or the hole transport layer. The hole injection layer or the hole transport layer may be formed of one or more of the above materials, or may be laminated and formed by a cavity injection hole or a hole transport layer. The film thickness of the hole injection layer or the hole transport layer is not particularly limited, and is preferably 20 to 2 00 nm (Organic semiconductor layer) The organic semiconductor layer is preferably a layer having a thickness of 1 〇'1 () S/cm or more for the hole injection or electron injection of the light-emitting layer. As the material, a conductive oligomer such as an arylamine-containing oligomer or a conductive polymer having an aromatic amine-containing dendrimer such as -34-200918638, which is described in the above-mentioned publication, can be used. Dendritic polymer, etc. The film thickness of the organic semiconductor layer is not particularly limited, but is preferably 1 〇 to i, oo 〇 nm. Electron injection/transport layer (electron transport region) is used as a second organic layer between the cathode and the luminescent layer. An electron injecting layer or an electron transporting layer may be provided. The electron injecting layer or the electron transporting layer is a layer that facilitates electron injection into the light emitting layer, and the electron mobility is large. The electron injecting layer is a rapid change in energy level, and the like. As a material used for the electron injecting layer or the electron transporting layer, a metal complex, an oxadiazole derivative, or a nitrogen-containing heterocyclic derivative of 8-hydroxyquinoline or a derivative thereof can be used. Above 8 Specific examples of the metal complex of hydroxyquinoline or a derivative thereof may be a chelated metal chelating oxynoid compound containing oxine (usually 8-quinolinol or 8-hydroxyquinoline), for example, ginseng may be used. (8-quinolinol) aluminum. The oxadiazole derivative may, for example, be an electron-transporting compound represented by the following general formula.

Ar20—^ Ar2

Ar23 —〇— Ar24

In the formula, Ar 'Ar18' Ar19' Ar21' Ar and Ar25 represent an aryl group having -35-200918638 with or without each substituent, and Ar17 and Ar18, Ar19 and Arn, Ar22 and Ar25 may be the same or different from each other. Ar2()' Ar23 and Ar24 represent an extended aryl group with or without each substituent 'Ar23 and Ar24 may be the same or different from each other. The aryl group of the above formula may, for example, be a phenyl group, a biphenyl group, a thiol group, a phenanthryl group or a fluorenyl group. Further, examples of the exoaryl group include a stretching phenyl group, a stretching naphthyl group, a stretching phenyl group, a stretching thiol group, a stretching group, and a stretching group. The substituents of the carbon number of 1 to 10, the decyloxy group having a carbon number of 1 to 1 Å, or a cyano group may be mentioned. The electron-transporting compound is preferably one having a good film formability. Specific examples of these electron-transporting compounds include the following.

The nitrogen-containing heterocyclic derivative may be a nitrogen-containing compound of a metal complex which is not composed of the following general formula 200918638.

(101) (102) That is, the nitrogen-containing compound which is a non-metal complex is a 5-membered ring or a 6-membered ring having a skeleton of the formula (101) or a skeleton represented by the formula (102). In the formula (102), X represents a carbon atom or a nitrogen atom. Zi and Z2 each independently represent a group of atoms which can form a nitrogen-containing hetero ring. (103) Preferably, the nitrogen-containing aromatic polycyclic group having a 5-membered ring or a 6-membered ring is an organic compound having a skeleton having a non-contiguous binding position when the plurality of nitrogen atoms are plural. Further, the case of the nitrogen-containing scented polycyclic group having such a plurality of nitrogen atoms is a nitrogen-containing aromatic polycyclic organic compound having a skeleton combining the above (101) and (102)).

A nitrogen-containing heterocyclic derivative containing a nitrogen-containing heterocyclic group of the formula 1 ° -37 - 200918638

Further, as a preferable specific compound, a nitrogen heterocyclic HAr-form containing -38-200918638 as shown in the following general formula, and L is a substituted substituent. Also a derivative. In a L1—Ar1-Ar2, HAr is a nitrogen-containing heterocyclic single bond having 3 to 40 carbon atoms which may have a substituent, and a carbon number of 6 to 40 or a carbon group which may have a substituent a heterocyclic aryl group of 3 to 4 Å, Ar 1 is a divalent aromatic hydrocarbon group which may have a substituent 6 〜, and Ar 2 is an aryl group which may have a substituent of 6 to 4 fluorene or a carbon number which may have a substituent of 3 to 40 The heteroaryl 'HAr is a nitrogen-containing heterocyclic derivative selected from the group consisting of the following. -39- 200918638

L is a nitrogen-containing heterocyclic derivative selected from the group consisting of the following.

Ar2 is a nitrogen-containing heterocyclic derivative selected from the group consisting of the following. -40- 200918638

Ar is a nitrogen-containing heterocyclic derivative having an arylsulfonyl group shown below

In the formula, R1 to R14 each independently represent a hydrogen atom, a halogen atom, a group having 1 to 2 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 40 carbon atoms, and may have a substituent. The aryl group having 6 to 40 carbon atoms or the heteroaryl group 'Ar3 having 3 to 40 carbon atoms is an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms which may have a substituent.

In Ar1, all of R1 to R8 are nitrogen-containing heterocyclic derivatives of a hydrogen atom. The nitrogen-containing heterocyclic derivative represented by the following formula can also be used as an electron injecting (transporting) material. -41 - 200918638

(ΙΑ) (IB) wherein Α1 to Α3 are a nitrogen atom or a carbon atom, the aryl group having a carbon number of 6 to 60 which may have a substituent, and a heteroaryl group having a carbon number of 3 to 6 Å which may have a substituent a group having a carbon number of 1 to 20, a halogen number of carbon number &~", an alkoxy group having a carbon number of 1 to 2 'n is an integer of 0 to 5, and when η is an integer of 2 or more, a plural number R They may be the same or different from each other. Further, the contiguous plural R groups may be bonded to each other to form a substituted or unsubstituted carbocyclic aliphatic ring, or a substituted or unsubstituted carbocyclic aromatic ring.

Ar1 is an aryl group having 6 to 60 carbon atoms which may have a substituent, a heteroaryl group having 3 to 60 carbon atoms which may have a substituent, and Ar2 is a hydrogen atom, an alkyl group having a carbon number of i to 2c, and a carbon number of 1 to 20 The haloalkyl group, the alkoxy group having a carbon number of 1 to 2 Å, the heterocyclic group which may have a substituent, a quinone, and an anthracene. However, in the case of At1 and Ar2, the condensed ring group having a carbon number of 10 to 60 having a substituent may be substituted with a heterocyclic ring group having a carbon number of 3 to 60 in place of the ruthenium. -42- 200918638

The basis of the base. a heterocondensed ring of a condensation 60 having a carbon number of 6 to 60 which may have a substituent or a nitrogen-containing hetero ring which may have a substituted HAr - L - Ar1 - Ar2 H Ar which may have a substituent of 3 to 4 carbon atoms, L a single bond, a aryl group having 6 to 6 carbon atoms which may have a substituent, a heteroaryl group having 3 to 6 carbon atoms which may have a substituent, or a stretching group which may have a substituent, and Ar may have The divalent aromatic hydrocarbon group 'Α' of the carbon number of 6 to 6 Å of the substituent is an aryl group having 6 to 60 carbon atoms which may have a substituent or a heteroaryl group having 3 to 60 carbon atoms which may have a substituent. Further, the following s-heterocyclopentadiene derivatives are also applicable to electron injecting (transporting) materials.

Wherein X and Y each independently represent a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a hydroxyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted hetero The ring or X combines with gamma to form a structure of a saturated or unsaturated ring.

Ri~R4 each independently represent hydrogen, halogen, substituted or unsubstituted alkyl, alkoxy, aryloxy, perfluoroalkyl, perfluoroalkoxy '-43-200918638 amine group Alkyl aryl, aryl ortho, oxycarbonyl, aryloxy azo, azo, aryloxy, oxyalkyloxy, aryloxysilane, A sulfonyl group, a sulfonyl group, a sulfanyl group, a fluorenyl group, an aminomethylmercapto group, an aryl group, a heterocyclic group, an alkenyl group, an alkynyl group, a nitro group, a fluorenyl group, A nitroso, a methyloxy group, an isocyano group, a cyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group or a cyano group or a structure in which a ring is condensed to a substituted or unsubstituted ring. However, when 1^ and R4 are a phenyl group, X and Y are not an alkyl group and a phenyl group, and when Ri and R4 are a thienyl group, X and Y are not simultaneously a monovalent hydrocarbon group, and R2 and R3 are an alkyl group or an aryl group. Alkenyl or R2 is bonded to R3 to form a structure of an aliphatic group of a ring. When Ri and R4 are a germyl group, R2, R3, X and Y are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom, R! And when R2 is a structure in which a benzene ring is condensed, X and Y are a non-alkyl group and a phenyl group. The boron compound derivative shown in the following formula can also be used as an electron injecting (transporting) material.

R5 R6 wherein Z2 and independently represent independently a hydrogen atom, a saturated or unsaturated hydrocarbon group, an aromatic group, a heterocyclic group, a substituted amine group, a substituted boron alkyl group, an alkoxy group or an aryloxy group, X, Y and ZI Each independently represents a saturated or unsaturated -44 - 200918638 hydrocarbon group, an aromatic group, a heterocyclic group, a substituted amino group, an alkoxy group or an aryloxy group, and the substituents of 2 and Z2 may be bonded to each other to form a condensed ring, and η represents An integer of 1 to 3, when η is 2 or more, 'Ζ, and Ζ2 can be different from each other. However, the case where η is 1 and Χ, Υ and 艮 2 are methyl groups, the uldent 8 is a hydrogen atom or a substituted boryl group, and η is 3 and Ζ is a methyl group. Further, the gallium dislocation shown in the following formula can also be used as an electron injecting (transporting) material. Q1\

Ga—L c / where 'Q1 and Q2 each independently represent a ligand represented by the following formula, L represents a dentate atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group. Aryl, substituted or unsubstituted heterocyclic group, 〇Ri (R 1 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted ring vh group substituted or unsubstituted aryl group, substituted or not Substituted heterocyclic group), Benz GaQ (Q4) (Q3 and Q4 Table 75 have the same meaning as V and Q2). In the formula, 'Q1 to Q4 are a quinoline residue such as 8-hydroxyindole_, 2_methyl-8-transpyrylation of a residue represented by the following formula, but are not limited thereto. A1 \ > C / -45- 200918638 Rings A1 and A2 are substituted or unsubstituted aryl ring or heterocyclic structures bonded to each other. The above-mentioned metal complex has strong properties as an n-type semiconductor and has a large electron injecting ability. Further, when the formation energy of the deformed body is also low, the metal-formed metal formed by the complex is also strongly bonded, and the fluorescence quantum efficiency as the light-emitting material also becomes large. Specific examples of the substituent of the ring A1 and A2 forming the ligand of the above formula include a halogen atom of chlorine, bromine, iodine, fluorine, a methyl group, an ethyl group, a propyl group, a butyl group, and a sec-butyl group. , substituted or unsubstituted alkyl, phenyl, naphthyl, tert-butyl, pentyl, hexyl, heptyl, octyl, stearyl, trichloromethyl, etc.

Substituted or unsubstituted aryl group of dichloromethylphenyl, 3-trifluoromethylphenyl, 3-nitrophenyl, etc., methoxy, n-butoxy, tert-butoxy, _ _ L chloromethoxy, dimethyl ethoxy 'pentafluoropropoxy, 2,2,3,3, fluoropropoxy, I'l'l'3'3,3-/, fluoro-2-propyl a substituted group of an oxy group, a 6-(perfluoroethyl)hexyloxy group or the like or a non-BV-substituted β- or unsubstituted anthracene t ^. an oxy group, a methoxy group, a P-nitrophenoxy group , P, a jasmine; ":,, Θ < -tert· phenoxy-substituted or unsubstituted aryloxy, methylthio, ethylthiothio, hexylthio, ^ ^ ^ Substituted or unsubstituted alkylthio group of octylthio group, trifluoromethylthio group, etc., butyl-based thio group, P-nitrophenylthio group, P-tert-" basic group Amine group, methylamino group, and unsubstituted aryl group of a thio group, a 3*S^^-fluorobenylthio-pentafluorophenylthio group, a 3-trifluoromethylidenethio group, or the like a mono- or di-substituted amine group such as a thio group, a cyano group, a nitro group, a dibutylamino group, a monoethylamino group, an ethylamino group, a dimethylamino group, a dipropylamino group, an amine group, or a bis(ethylene oxide) base Gaso-oxyl, pentafluorophenyl, 3-trifluoromethylphenoxy, etc., tert--46-200918638 methyl)amine, bis(ethyloxyethyl)amine, bisacetoxy A) anthranyl, bis(acetoxybutyl)amino and the like guanylamino, cumyl, methyl 7 alkoxy, decyl, methylaminomethyl, dimethylaminomethyl, ethyl Aminomethyl fluorenyl, carboxylic acid group, sulfonic acid group, imino group, such as aminomethyl hydrazino, diethylaminomethyl hydrazino, propylaminomethyl decyl, butylaminomethylase, anilinomethyl decyl An alkyl group such as a cyclopentyl group or a cyclohexyl group, an aryl group such as a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl 'phenanthryl group, an anthranyl group or a fluorenyl group, a pyridyl group, a pyrazinyl group or a pyridyl group. , pyridazinyl, triazinyl, fluorenyl, quinolyl, acridinyl, succinyl, dioxoalkyl, piperidinyl, morpholinyl, piperazinyl, oxazolyl, succinyl a heterocyclic group such as a thiol group, a thienyl group, an oxazolyl group, an oxadiazolyl group, a benzoxazolyl group, a thioxanyl group, a thiadiazolyl 'benzothiazolyl group, a triazolyl group, an imidazolyl group, a benzimidazolyl group, etc. . Further, the above substituents may be further bonded to each other to form a aryl ring or a heterocyclic ring. In the other, the following organic compound which satisfies the conditions of the element described above, which is described in JP-A-9-3448, can be mentioned.

1 R4 each independently represents a hydrogen atom, a substituted aliphatic group, a substituted or unsubstituted aliphatic cyclic group: an unsubstituted aliphatic carbocyclic aromatic ring group, a substituted or unsubstituted heterocyclic group or unsubstituted Stands for an oxygen atom, a sulfur atom or a dicyanomethyl group. Further, the following organic compounds satisfying the above-described element constitution conditions described in JP-A No. 2,0--73,774, are also available.

However, in the above general formula, R1, R2, R3 and R4 are the same or different groups, and are aryl groups represented by the following general formula.

R8 R9 R6 R5 R7 However, in the above general formula, 'R5, R6, R7, R8 and R9 are the same or different from each other, a hydrogen atom, or at least one of them is a saturated or unsaturated alkoxy group, an alkane Base, amine or alkylamine group. Further, it may be a high molecular compound containing the nitrogen-containing heterocyclic group or the nitrogen-containing heterocyclic derivative. The film thickness of the electron injecting layer or the electron transporting layer is not particularly limited, but is preferably 1 to 1 〇 〇 n m. The first luminescent layer or the first organic layer closest to the organic layer of the anode is preferably one containing an oxidizing agent. The preferred oxidant contained in the first luminescent layer or the first organic layer is an electron attracting or electron acceptor. Preferred are Lewis acid, various -48-200918638 acid derivatives, dicyano-p-dioxane derivatives, salts of aromatic amines and Lewis acids. It is particularly preferred that the Lewis acid is a gas, a chlorinated metal, a chlorinated metal, or an aluminum chloride. The light-emitting layer or the second organic layer closest to the organic layer of the cathode is preferably one containing a reducing agent. Preferred reducing agents are alkali metal, alkaline earth metal, alkali metal oxide, alkaline earth oxide, rare earth oxide, alkali metal halide, alkaline earth halide, rare earth halide, alkali metal and aromatic compound. The wrong body. Particularly preferred alkali metals are Cs, Li, Na, and K. In a preferred embodiment of the organic EL device, there is a region in which electrons are transported or an interface region between the cathode and the organic layer contains a reducing blend. Here, the reducing blend is defined as a substance capable of reducing an electron transporting compound. Therefore, various types can be used only for those having a certain degree of reduction. For example, at least one selected from the group consisting of an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, and a soil test metal can be used. a group of oxides, alkaline earth metal halides, rare earth metal oxides or rare earth metal halides, alkali metal organic compounds, alkaline earth metal organic compounds, and rare earth metals Substance. Further, as a more specific preferred reductive blend, Li (work function: 2.9 eV), Na (work function: 2.36 eV), K (work function: 2.28 eV), and Rb (work function: 2.16eV) and Cs (work function: l_95eV) are at least one alkali metal group, or selected from ca (work function: 2.9eV), sr (work function: 2.0 to 2.5eV), and Ba (work function: It is particularly preferable that the work function of at least one alkaline earth metal in the group of 2.52 eV) is 2.9 eV or less. Preferred reductive blends thereof are selected from the group consisting of K, Rb and -49- 200918638

At least one alkali metal in which Cs is grouped, more preferably Rb 3 Cs. These alkali metals are extremely high in reducing ability, and the illuminating brightness in the organic EL element can be achieved by a small injection area. Further, it is preferable to use a combination of two or more kinds of alkali metals having a work function of 2.9 eV or less, and it is preferable to contain Cs, for example, Cs and Na, Cs and K, and Cs and Rb or Cs are preferably combined. By combining the inclusion of Cs, it is possible to efficiently increase the brightness of the organic light or to extend the life by adding the electron injecting region. An electron injecting layer of an insulator may be further disposed between the cathode and the organic layer. At this time, the electron injectability of the current is effectively prevented. As such an insulator, at least one metal compound selected from the group consisting of an alkali, an alkaline earth metal chalcogenide, an alkali metal halide, and a halide is preferably used. It is composed of these alkali metal chalcogenides and the like, and is preferably further preferred. As a specific preferred alkali metal chalcogenide, Li20, K20, Na2S, Na2Se and Na20 are exemplified as the chalcogenide, and examples thereof include CaO, BaO, SrO' and C a S e . Further, examples of the preferred halide of an alkali metal include NaF, KF, LiCl, KC1, and NaCl. Further, examples of the metal halide include a fluoride of CaF2, BaF2, and BeF2, or a halide other than a fluoride. Further, as the semiconductor constituting the electron transport layer, one selected from Ba, Ca, Sr, Yb, Al, Ga, In, and C s is preferably added in an amount of an electron-increasing or long-lived blend. The combination can be particularly good and Na and K can reduce the ability of the EL element or the leakage of the semiconductor structure, and the electron injecting layer of the metal chalcogenide alkaline earth metal can be improved to increase the electronic injection only, for example, a better test is possible. Soil gold ' BeO, BaS, such as L i F is a better soil test type rF2, MgF2 and cites at least "i, N a, C d, -50- 200918638

One or a combination of two or more kinds of oxides, nitrides, or oxynitrides of the elements of Mg, Si, Ta, Sb, and Zn. Further, it is preferable that the inorganic compound constituting the electron transport layer is a microcrystalline or amorphous insulating film. The electric + transport layer may be composed only of these insulating films, and a more homogeneous film may be formed to reduce black spots and the like. Pixel defects. Further, examples of the inorganic compound include the above-mentioned alkali metal chalcogenide, alkaline earth metal chalcogenide, alkali metal halide, and alkaline earth metal tooth. (Cathode) As the cathode, in order to inject electrons into the electron injecting/transporting layer or the light-emitting layer, a metal having a small work function (4 eV or less), an alloy, an electrically conductive compound, or a mixture thereof may be used as the electrode material. Specific examples of such an electrode material include sodium, a sodium-potassium alloy, magnesium, lithium, magnesium, a silver alloy, aluminum/aluminum oxide, an aluminum-lithium alloy, indium, and a rare earth metal. The cathode can be produced by forming a thin film by vapor deposition or sputtering. When the light emission from the light-emitting layer is taken out from the cathode, it is preferable that the transmittance of the light emission of the cathode is larger than 10%. Further, the sheet resistance of the cathode is preferably several hundred Ω/□ or less, and the thickness is generally from 10 nm to Ιμηη, preferably from 50 to 2 〇〇 nm. (Insulating layer) Since the organic EL has an electric field applied to the ultra-thin film, it is liable to cause pixel defects due to electric leakage or short circuit. To prevent this, it is preferable to insert an insulating layer between the pair of electrodes -51 - 200918638. Examples of the material used for the insulating layer include lithium oxychloride, lithium oxide, fluorinated planer, oxidized planer, magnesium oxide, fluorinated, calcium fluoride, aluminum nitride, titanium oxide, cerium oxide, and cerium nitride boron nitride. , molybdenum oxide, cerium oxide, palladium oxide, and the like. Mixtures or laminates thereof may also be used. [Method of Manufacturing Organic EL Element] Next, a method of manufacturing the organic EL element will be described. The anode is formed by the above-exemplified materials and formation methods. It is necessary to form a hole injection layer, and if necessary, to form an electron injection, and further to form a cathode, an organic EL element can be produced. Further, an organic EL element can be produced in the reverse order of the above-described procedure. Hereinafter, an organic EL example in which an anode/cavity is injected into the electron injection layer/cathode in the order of the light-transmissive substrate is described. First, an anode material is formed by vapor deposition or sputtering on a suitable light-transmitting substrate to a thickness of Ιμηι or less, preferably in a range of film thicknesses to form an anode. Next, a hole injection layer is provided on the anode. The formation of the hole injection layer can be carried out by a vacuum evaporation method, a rotary injection method, or an LB method. It is preferably selected from the range of film thickness. Secondly, the shaped aluminum, magnesium fluoride, oxidized, nitriding sand, luminescent layer and in-layer of the luminescent layer disposed on the injection layer of the hole are formed by the cathode to the cation layer/light-emitting layer/element The film is made by 10~200nm transfer coating method, 5 nm ~ 5 μπι can be used -52-200918638 organic light-emitting material by means of vacuum evaporation method, or __ coating method, pouring method The organic light-emitting material is formed by thinning after the wet process. Next, an electron injecting layer is provided on the light emitting layer. An example of formation by a vacuum vapor deposition method is mentioned. After the final cathode is laminated, an organic EL element can be obtained. Since the cathode is made of metal, vapor deposition or sputtering can be used. However, it is preferable that the organic layer for protecting the substrate in the film formation is not damaged, and vacuum evaporation is preferred. The method of forming each layer of the organic EL element is not particularly limited. A method of forming a vacuum vapor deposition method, a spin coating method, or the like, which is known in the art, may be used, that is, the organic thin film layer may be subjected to a vacuum evaporation method, a molecule, a wire evaporation method (MBE method) or a solution dissolved in a solvent. Dipping method, rotating coated cloth? A coating method such as a dropping, casting, bar coating, roll coating, or inkjet method is formed by a known method. The thickness of each organic layer of the organic EL element is not particularly limited. However, when the film thickness is too thin, defects such as pinholes are likely to occur, and if it is too thick, a high applied voltage is required, and the efficiency is deteriorated. Therefore, the range of several nm to Ιμιη is generally preferred. Further, when a DC voltage is applied to the organic EL element, the anode is made to be +, the cathode is used as the polarity of -, and the voltage of 5 to 40 V is applied to observe the light emission. Further, even if a voltage is applied in the opposite polarity, the current does not flow, and no light is generated at all. Further, when an AC voltage is applied, only the anode becomes +, and the cathode becomes a polarity of -, and uniform light emission can be observed. Additional AC waveform -53- 200918638 is optional. [Embodiment] [Embodiment] Next, an embodiment of the present invention will be described. [Composition of sample] First, the configuration of the sample will be described. (Example 1) A glass substrate (manufactured by Geomatics Co., Ltd.) to which an ITO transparent electrode (anode) having a thickness of 25 mm x 75 mm x 1. lmm was attached was ultrasonically washed in isopropyl alcohol for 5 minutes, and then washed by UV ozone. minute. The washed glass substrate with the transparent electrode wire is assembled on the substrate holder of the vacuum evaporation apparatus, and the following compound is formed on the side of the transparent electrode line, for example, by covering the transparent electrode. A-1. Further, the following compound H-1 and the following compound D-1 were formed into a film having a film thickness of 40 nm at a film thickness ratio of 40:2 on the A-1 film to obtain a blue light-emitting layer. Compound H-1 can be used as a main component, and D-1 can function as a blend. On the film, Alq was deposited as an electron transport layer by vapor deposition of the following structure to a film thickness of 20 nm. Thereafter, LiF was formed into a film having a film thickness of 1 nm. On the LiF film, the metal A1 was evaporated to 150 nm to form a metal cathode to form an organic EL device. -54- 200918638

(Example 2) In Example 1, an organic EL device was produced in the same manner as in the case of D-2 having the following structure in place of D-1.

(Example 3) In Example 1, D-3 of the following structure was used instead of D-1, and an organic EL device was produced in the same manner. -55- 200918638

(Example 4) In Example 1, D-4 was used instead of D-1, and an organic EL element was produced in the same manner.

Method to produce organic EL components and the same -56- 200918638

(Example 6) In Example 1, D-6 was used instead of D-1, and an organic EL element was produced by the same method.

(Example 7) In Example 1, D-7 was used instead of D-1, and an organic EL device was produced in the same manner.

(Example 8) -57-200918638 In Example 1, an organic EL device was produced in the same manner as in the case of D-8 having the following structure in place of D-1.

(Example 9) In Example 1, an organic EL device was produced in the same manner as in the case of D-1 having the following structure in place of D-1.

(Example 1 〇) In Example 1, an organic EL device was produced in the same manner as in the case of H-2 having the following structure in place of H-1. -58- 200918638

(Example 1 1) In Example 1, an organic EL device was produced in the same manner as in the case of using H-3 having the following structure in place of hydrazine-1.

(Example 1 2) In Example 1, an organic EL device was produced in the same manner as in the case of using Η-4 having the following structure instead of Η-1.

(Example 1 3) -59-200918638 In Example 1, an organic EL device was produced in the same manner as in the case of H-5 having the following structure in place of hydrazine-1.

(Example 1 4) In Example 1, an organic EL element was produced in the same manner as in the above-mentioned method using H-6 of the following structure.

(Comparative Example 1) In Example 1, the compound (A) having the following structure was used instead of D-1, and an organic EL device was produced in the same manner. -60- 200918638

(Comparative Example 2) In Example 1, a compound (B) having the following structure was used instead of D-1, and an organic EL device was produced in the same manner.

(Comparative Example 3) In Example 1, a compound (C) having the following structure was used instead of hydrazine-1, and an organic EL device was produced in the same manner.

-61 - 200918638 [Evaluation method] Next, explain the evaluation method. In the organic EL devices of the above Examples 1 to 14 and Comparative Examples 1 to 3, the external quantum yield, the emission wavelength, and the initial luminance of 300 cd/m 2 of the device performance at the time of driving current density of 1 〇 mA/cm 2 were measured. half life. These results are shown in Table 1. Further, the physical properties of the main material and the blend material of the examples used are shown in Table 2. [Table 1]

515 does not obtain the luminescence of D 1 -62- 200918638 m 2] Affinity level admixture of the energy component of the main component of the main material - the affinity of the energy gap of the blend Example 1 H-1 3.2 2.6 ~--- D-1 3.1 2.4 Example 2 H-1 3.2 2.6 '-, D-2 _ 3.1 2.4 Example 3 H-1 3.2 2.6 --- D-3 3.0 2.4 Example 4 H-1 3.2 2.6 ^----^ D-4 _ 3.1 2.4 Example 5 H-1 3.2 2.6 --- D-5 3.1 2.4 Example 6 H-1 3.2 2.6 D-6 3.0 2.5 Example? H-1 3.2 2.6 D -7 _ 3.0 2.5 Example 8 H-1 3.2 2.6 - D-8 .3.0 2.5 Example 9 H-1 3.2 2.6 D-9 3.0 2 5 Example 10 H-2 3.2 2.6 D-1 3.1 2 4 Example Π H-3 3.2 2.6 D-1 3.1 2 4 Example 12 H-4 3.2 2.6 D-1 3.1 2 4 Example 13 H-5 3.2 2.6 D-1 3.1 2.4 Example 14 H-6 3.2 2.6 D-1 3.1 2.4 Comparative Example 1 H-1 3.2 2.6 (A) 2.8 2.7 Comparative Example 2 H-1 3.2 2.6 (B) 2.7 2.7 Comparative Example 3 (C) 3.0 3.0 D-1 3.1 2.4 [Evaluation Results] As shown in Table 1 For the external quantum yield, it was confirmed that there was not much difference between Examples 1 to 14 and Comparative Examples 1 and 2. Further, with respect to the emission wavelength, it was confirmed that Examples 1 to 14 showed shorter wavelengths than Comparative Examples 1 to 2. Further, for the lifetime, it was confirmed that Examples 1 to 14 were twice as long as those of Comparative Examples 1 and 2. Further, in Comparative Example 3, since the energy gap of the main component was smaller than the energy gap of the blend, the light emission from the blend could not be obtained. In the case of using the light-emitting layer of the present invention, it has been confirmed that an organic EL element having a short-wavelength and a long-life of the blue light-emitting wavelength can be obtained, and is described in Document 1 (JP-A-2004-75567). An organic EL device having an oligo-aromatic derivative as a main component material and an arylamine compound or a styrylamine compound as a light-emitting layer of a blend. As an oligo-extension derivative, it has been revealed that the cave is the central skeleton. However, the illuminating wavelength of the admixture of the mixture D 1 (phenethylamine compound) used in the embodiment 9 and the embodiment 11 shown in the literature is different from the blend constituting the organic EL element of the present invention. It is not sufficiently short and the life expectancy has not been sufficiently improved. Further, in the blend D 2 (arylamine compound) used in Example 1 and Example 12, since the central skeleton is ruthenium, the central skeleton of the present invention is selected from substituted or unsubstituted benzene, Compared with naphthalene, anthracene and phenanthrene, the emission wavelength is longer, and the object of the present invention is not achieved. Therefore, the short-wavelength luminescence of the combination of the main component and the blend of the present invention is not able to obtain a long-life effect. -64 -

Claims (1)

200918638 X. Patent Application No. 1 - An organic EL device which is an organic thin film layer formed by sandwiching a layer or a plurality of layers containing at least a light-emitting layer between a cathode and an anode, wherein the light-emitting layer is generally The main component shown in the formula (1) and the τ ρ: complex formed by the following formula (2), (In the general formula (1), R1 to R12 represent a hydrogen atom or a substituent; but at least one of 'R1 to R12' independently represents a substituted or unsubstituted aryl group having a core carbon number of 6 to 60) (In the general formula (2), Ar1 to Ar4 each independently represent an unsubstituted or unsubstituted aryl group having a core carbon number of 6 to 14; and Li represents a substituted or unsubstituted benzene skeleton, a naphthalene skeleton, an anthracene skeleton, a phenanthrene, -65 - 200918638 Skeleton; p is an integer from 1 to 6' When P is 2 or more, 1^ may be the same or different from each other; 7 'P is 2 or more, and the substitution positions of L1 may be the same or different, s is 0 or 1). 2. The organic EL device according to claim 1, wherein the biologic compound is substituted for the above general formula (2)' which is represented by the following general formula (3); • (3) (General formula C 3 ), a"~a〆 each independently represents a substituted or unsubstituted phenyl, naphthyl, sin. L2, L3 each independently substituted or unsubstituted benzene skeleton , naphthalene skeleton, phenanthrene skeleton). 3. For example, the organic EL element of the patent or the second item, wherein the main component is as shown in the following formula (4), Ar9-Ch-Ar10-66-* (4) 200918638 Skeleton, substituted or unsubstituted aryl (in general formula (4), Ch represents a substitution or no Ar9, and ArIG each independently represents a substituent consisting of a single or plural combination of a core having 6 to 14 carbon atoms). -67- 200918638 VII. Designated representative map (1) The designated representative figure of this case is: None (2). The representative symbol of the representative figure is a simple description: No. 8. If there is a chemical formula in this case, please reveal the characteristics that can best show the invention. Chemical formula: none